1

Chapter 16
More Equilibria in Aqueous Solution
Slightly Soluble Salts
&
Complex Ions
Hill, Petrucci, McCreary & Perry 4
th
Ed.
The Solubility Product Expression
Solubility Equilibria are Heterogeneous
Equilibria.
Calcium Oxalate:
CaC
2
O
4(s)
Ca
2+
(aq)
+ C
2
O
4
2-
(aq)
K
sp
= [Ca
2+
][C
2
O
4
2-
]
Lead Iodide:
PbI
2(s)
Pb
2+
(aq) +
2 I
-
(aq)
K
sp
= [Pb
2+
][I
-
]
2
The exponents are equal
to the coefficients
Write the K
sp
Expression from the
Chemical Equation!
Hg
2
Cl
2(s)
Hg
2
2+
(aq)
+ 2 Cl
-
(aq)
K
sp
= [Hg
2
2+
][Cl
-
]
2
Mercury (I) is a dimeric ion!
HgCl
2(s)
Hg
2+
(aq)
+ 2 Cl
-
(aq)
K
sp
= [Hg
2+
][Cl
-
]
2
Mercury (II) is a monomeric ion!
2
Calculating K
sp
from Solubility
Silver Chloride, AgCl, has a solubility of 1.9 x
10
-3
g/L calculate the solubility product.
Calculating K
sp
from Solubility
Lead Iodide, PbI
2
, has a solubility of 1.2 x 10
-3
mol/L calculate the solubility product.
Calculating Solubility from Ksp
Calculate the molar solubility of Calcium
Fluoride, CaF
2
, from its Ksp of 3.4 x 10
-11
.
CaF
2(s)
Ca
2+
(aq)
+ 2 F
-
(aq)
-x +x +2x
K
sp
= [Ca
2+
][F
-
]
2 solve the K
sp
expression for x!
3
Solubility and the Common Ion Effect
CaC
2
O
4(s)
Ca
2+
(aq) + C
2
O
4
2-
(aq)
The dissociation/dissolution of Calcium Oxalate.
In pure water: Ksp = 2.7 x 10
-9
-x +x +x
[ ]
eq1 ~
~
0
Adding a soluble calcium salt such as CaCl
2
so [Ca
2+
] =
0.15 M we will shift the equilibrium to the left. Calcium
oxalate will become less soluble in the solution of Ca
2+
.
[ ]
eq2
-z
0.15 + z +z
~
~
0
~
~
0.15 M
It should be clear that z < x << 0.15, i.e. both are near zero
compared to the much larger concentration of calcium ion.
Solubility and the Common Ion Effect
Calculate the solubility of calcium oxalate
In pure water:
CaC
2
O
4(s)
Ca
2+
(aq) + C
2
O
4
2-
(aq)
-x +x +x [ ]
eq1 ~
~
0
K
sp
= [Ca
2+
][C
2
O
4
2-
]
Now in 0.15 M CaCl
2
:
[ ]
eq2
-z 0.15 + z +z
~
~
0
~
~
0.15 M
K
sp
= [Ca
2+
][C
2
O
4
2-
]
Knowing When a Precipitate will Form
Precipitation occurs when Q
sp
the ion
concentration product exceeds K
sp
.
Q
sp
< K
sp
=> Unsaturated
Q
sp
= K
sp
=> Saturated
Q
sp
> K
sp
=> Supersaturated
A supersaturated solution is not at
equilibrium but is metastable and will
form a precipitate on initiation.
4
Will a Precipitate Form?
A solution containing 0.0052 M Calcium ion and 0.0041 M
sulfate ion in solution was evaporated to half its original
volume. Will a precipitate form?
K
sp
= 2.4 x 10
-5
Ca
2+
(aq)
+ SO
4
2-
(aq)
CaSO
4(s)
Concentrations
before evaporation!
0.0052 M 0.0041 M
K
sp
= [Ca
2+
][SO
4
2-
] = 2.4 x 10
-5
At equilibrium!
Concentrations
after evaporation?
Will a Precipitate Form?
255 mL of 0.00016 M lead nitrate solution and
456 mL of 0.00023 M sodium sulfate solution are
combined. Will a precipitate form?
Pb
2+
(aq) + SO
4
2-
(aq)
PbSO
4(s)
K
sp
= 1.7 x 10
-8
K
sp
= [Pb
2+
][SO
4
2-
] = 1.7 x 10
-8
[Pb
2+
] =
[SO
4
2-
] =
Calculating these concentrations is a dilution problem!
Q
sp
= ?
Determining Completeness of Precipitation
Usually one ion is added, as a soluble salt,
to another ion to cause precipitation. The
amount of precipitate is usually a problem
in reaction stoichiometry.
It is often necessary to determine the
residual ion concentration and the percent
removed as the precipitate which formed.
This requires use of the solubility product
expression to determine concentration of
the residual ion.
5
Determining Completeness of Precipitation
500 mL of 1.0 x 10
-3
M potassium chromate solution and
500 mL of 1.0 x 10
-5
M lead acetate solution are combined.
Calculate amount of precipitate formed?
Pb
2+
(aq) + CrO
4
2-
(aq)
PbCrO
4(s)
K
sp
= 1.8 x 10
-15
K
sp
= [Pb
2+
][CrO
4
2-
] = 1.8 x 10
-15
The quantity of lead ion is clearly the limiting reactant!
Use stoichiometry to calculate the quantity of lead
which will precipitate! Assume 100% precipitation!
Use the concentration of excess chromate ion to calculate
the concentration of residual lead ion in the solution!
Can we approximate [CrO
4
2-
] ? Don't forget the effect of
dilution on the concentrations here!
The Effect of pH on Solubility
If a salt is a slightly soluble metal hydroxide
lowering the pH (reducing the hydroxide
concentration) makes it more soluble; dissolve;
and conversely.
If a slightly soluble salt has the anion of a weak
acid, lowering the pH will make it more soluble;
dissolve; and conversely.
If a slightly soluble salt has the cation of a weak
base, raising the pH will make it more soluble;
dissolve; and conversely.
pH and Solubility
Calculate the pH of a saturated solution of Magnesium
Hydroxide, Mg(OH)
2
.
K
sp
= 1.8 x 10
-11
Mg(OH)
2(s)
Mg
2+
(aq)
+ 2 OH
-
(aq)
-x +x +2x
K
sp
= [Mg
2+
][OH
-
]
2

6
pH and Solubility
Calculate the maximum pH a 0.010 M solution of Magnesium
Chloride, MgCl
2
, a very soluble salt can be kept in solution.
The only ions present are Mg
2+
, Cl
-
, H
+
and OH
-
.
What is the only possible precipitate?
Write the chemical equation and the K
sp
expression.
Mg(OH)
2(s)
Mg
2+
(aq)
+ 2 OH
-
(aq)
K
sp
= [Mg
2+
][OH
-
]
2
= 1.8 x 10
-11

-x +x +2x
pH & Solubility of Metal Sulfides
Qualitative treatment of Principles of Qualitative Analysis.
H
2
S
(aq)
HS
-
(aq)
+ H
+
(aq)
S
2-
(aq)
HS
-
(aq)
+ H
+
(aq)
K
a
1
= 8.9 x 10
-8

K
a
2
= 1.2 x 10
-13

Control of sulfide ion concentration.
[H
2
S] = 0.10 M
saturated water at 25 C:
S
2-
(aq)
H
2
S
(aq)
+ 2 H
+
(aq)
K
a
1
,
2
=
[S
2-
] [H
+
]
2
[H
2
S]
= K
a
1

x K
a
2

= (8.9 x 10
-8
)(1.2 x 10
-13
)
[S
2-
] =
K
a
1
,
2

[H
+
]
2
[H
2
S]
1.1 x 10
-21
[S
2-
] =
[H
+
]
2
The [S
2-
] can be varied over
a wide range by control of pH.
[S
2-
] =
pH = 10
0.11
7
1 x 10
-7
1 x 10
-17
2
Most HS
-
salts of metal
ions are relatively soluble.
pH & Solubility of Metal Sulfides
The solubility of iron(II) sulfide is pH dependent.
FeS
(S)
Fe
2+
(aq)
+ S
2-
(aq)
K
sp
= 6 x 10
-18
K
sp
= [Fe
2+
][S
2-
] = 6 x 10
-18
[S
2-
]
[Fe
2+
] =
6 x 10
-18
and
1.1 x 10
-21
[S
2-
] =
[H
+
]
2
Assuming [H
2
S] is a 25 C
saturated solution = 0.10 M
Solubility at pH 1:
1 x 10
-19
[Fe
2+
] =
6 x 10
-18
[Fe
2+
] = 60 M
Very soluble!
Solubility at pH 7:
1 x 10
-7
[Fe
2+
] =
6 x 10
-18
[Fe
2+
] = 6 x 10
-11
M
Very insoluble!
Since the [S
2-
] can be varied over a wide range by control of pH the
solubility of most slightly soluble metal sulfides can be drastically changed.
7
pH & Solubility Selective Precipitation
Find a pH where only one of the two metals will precipitate
when [Fe
2+
] and [Cu
2+
] have concentrations of 0.050 M.
FeS
(s)
K
sp
= 6 x 10
-18
K
sp
= 6 x 10
-36
CuS
(s)
Relatively much more soluble! Relatively very insoluble!
Find a pH which will cause the relatively more soluble
salt to just become saturated.
This will not actually cause it to precipitate,
only reach its maximum limit of solubility.
The very insoluble salt will have precipitated and it is
possible to calculate its residual ion concentration.
Solubility Fractional Precipitation
Can barium, Ba
2+
, and strontium, Sr
2+
, be separated by
precipitation when both have concentrations of 0.100 M?
One needs to choose a precipitating anion that has a large K
sp

difference between the two cations, i.e. chromate!
BaCrO
4(s)
K
sp
= 1.2 x 10
-10
K
sp
= 3.5 x 10
-5
SrCrO
4(s)
Relatively very insoluble! Relatively much more soluble!
The experimental procedure is to titrate the solution with chromate
ion from a buret until the less soluble salt is precipitated.
If the Ksp difference is large enough there will be a pause of a few
drops as the concentration builds to saturate the more soluble salt.
The titration is stopped at this point and the precipitate is filtered.
The more soluble salt can now be precipitated without contamination.
The salts are now separated.
Mathematically one calculates the concentration of chromate ion
which will saturate the more soluble strontium ion. Then calculates
the residual barium ion remaining in solution at that concentration.